Electrode material for lithium-ion secondary battery, method for manufacturing same, electrode for lithium-ion secondary battery, and lithium-ion secondary battery

Patent metadata

Field	Value
Publication number	US-9960426-B2
Application number	US-201715470337-A
Country	US
Kind code	B2
Filing date	Mar 27, 2017
Priority date	Sep 30, 2016
Publication date	May 1, 2018
Grant date	May 1, 2018

Abstract

An electrode material for a lithium-ion secondary battery of the present invention is secondary particles including inorganic particles represented by General Formula LiFe x Mn 1-x-y M y PO 4 and a carbonaceous film coating surfaces of the inorganic particles, in which an amount of carbon is 0.5% by mass to 2.5% by mass, a specific surface area is 10 m 2 /g to 20 m 2 /g, a first particle diameter (D90(a)) at which a cumulative volume percentage of a particle size distribution of secondary particles is 90% before an ultrasonic treatment is 20 mm to 40 mm, a second particle diameter (D90(b)) at which the cumulative volume percentage of the particle size distribution of the secondary particles is 90% after the ultrasonic treatment is 10 mm to 15 mm, and a ratio (D90(b)/D90(a)) of the second particle diameter (D90(b)) to the first particle diameter (D90(a)) is 0.3 to 0.5.

First claim

What is claimed is:

1. An electrode material for a lithium-ion secondary battery which is secondary particles including: inorganic particles represented by General Formula LiFe x Mn 1-x-y M y PO 4 , wherein M represents at least one element selected from Mg, Ca, Co, Sr, Ba, Ti, Zn, B, Al, Ga, In, Si, Ge, and rare earth elements, 0.05≤x≤1.0, 0≤y≤0.14, and 0≤1−x−y; and a carbonaceous film that coats surfaces of the inorganic particles,
wherein an amount of carbon is 0.5% by mass to 2.5% by mass,
a specific surface area is 10 m 2 /g to 20 m 2 /g,
a first particle diameter (D90(a)) at which a cumulative volume percentage of a particle size distribution of secondary particles is 90% before an ultrasonic treatment is 20 μm to 40 μm,
a second particle diameter (D90(b)) at which the cumulative volume percentage of the particle size distribution of the secondary particles is 90% after the ultrasonic treatment is 10 μm to 15 μm,
a ratio (D90(b)/D90(a)) of the second particle diameter (D90(b)) to the first particle diameter (D90(a)) is 0.3 to 0.5 and
the ultrasonic treatment is carried out by a following method under a condition of the ultrasonic treatment shown below:
the ultrasonic treatment is carried out in an ultrasonic dispersion step in a circulation system of a laser diffraction and scattering particle size distribution analyzer LA-950V2 manufactured by Horiba Ltd;
wherein an ultrasonic intensity in the step is controlled using a software, the ultrasonic treatment is carried out with an intensity, wherein an intensity of the analyzer is capable of setting in a range of 0 to 7, set to 7, a power is set to 30 W, a frequency is set to 20 kHz, and a ultrasonic treatment time is set to 20 seconds excluding a time for a particle size distribution measurement: and the particle size distribution is measured with 50 g of water and the 1 mg of secondary particles injected into a sample injection opening.

2. The electrode material for a lithium-ion secondary battery according to claim 1 ,
wherein N-methyl-2-pyrrolidone is used as a solvent, and a traverse relaxation time measured using a nuclear magnetic resonance method is 40 ms to 400 ms, and the traverse relaxation time is measured by a following method under a condition shown below: 0.01 g of the electrode material for a lithium-ion secondary battery is weighed in a screw tube having a capacity of 30 mL, 10 g of N-methyl-2-pyrrolidone is added to the screw tube, and then an ultrasonic treatment is carried out for five minutes using an ultrasonic cleaning machine, thereby preparing a dispersion liquid including the electrode material for a lithium-ion secondary battery; the dispersion liquid is collected into an NMR tube, and the traverse relaxation time of the electrode material for a lithium-ion secondary battery is measured using a nuclear magnetic resonance device.

3. An electrode for a lithium-ion secondary battery comprising:
the electrode material for a lithium-ion secondary battery according to claim 1 .

4. A lithium-ion secondary battery comprising:
a cathode;
an anode; and
a non-aqueous electrolyte,
wherein the cathode is the electrode for a lithium-ion secondary battery according to claim 3 .

5. A method for manufacturing the electrode material for a lithium-ion secondary battery according to claim 1 , the method comprising:
a step of synthesizing LiFe x Mn 1-x-y M y PO 4 particles under pressure by heating raw material slurry α obtained by mixing an Li source, a Fe source, an Mn source, a P source, and an M source with a solvent including water as a main component; and
a step of coating surfaces of the LiFe x Mn 1-x-y M y PO 4 particles with a carbonaceous film by drying raw material slurry β formed by dispersing the LiFe x Mn 1-x-y M y PO 4 particles in a water solvent including a carbon source so as to granulate the slurry, then, preliminarily calcinating the granulated body so as to pulverize the granulated body, and then heating the pulverized body.

Assignees

• Sumitomo Osaka Cement Co Ltd

Inventors

• Yasumiishi Hirofumi
• Yamaya Ryuuta

Classifications

• H01M4/136

  Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy · CPC title

• H01M4/625

  Carbon or graphite · CPC title

• H01M4/1397

  of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M4/5825 Primary

  Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines · CPC title